JP2020172626A - Morphology modified heterophase propylene copolymers and products thereof - Google Patents

Abstract

To provide a PP composition of having the highest impact resistance of no-break along with a higher melt flow without affecting the flexural modulus.SOLUTION: The present invention provides a morphology modified heterophase polymer having a no-break impact strength of 500 J/m-700 J/m as per ASTM standard D256, a high melt flow index of 100 g/10 min as per ASTM D1238, and a balanced flexural modulus as per ASTM standard D790. More specifically, the present invention relates to a process for modification of morphology of a heterophase propylene polymer in the presence of an initiator in the form of organic peroxide and a multifunctional unsaturated organic vinyl compound on an ex-reactor heterophase propylene copolymer powder and/or a pellet using a special extrusion device.SELECTED DRAWING: None

Description

The present invention relates to morphologically modified heterophase polymers. In particular, the present invention relates to methods of modifying the morphology of heterophase propylene polymers in the presence of initiators and polyfunctional compounds / additives on ex-reactor polypropylene copolymers. More specifically, a morphologically modified heterophase polymer / heterophase propylene copolymer with a higher melt flow index, with no-break impact resistance as defined by a notched Izod test at room temperature. How to get it will be explained.

One of the recent trends in product development is polypropylene (PP) systems that contain three or more dispersed phases. The design concept of such a mixture is to select sub-ingredients in such a way that the strengths of one make up for the weaknesses of the other. Due to the temperature dependence of the deformation mechanism, the optimum particle size for polypropylene toughness decreases with increasing temperature, so the duality of dispersed phase size is a promising approach for ensuring toughness over a wide temperature range. obtain.

Product development begins with simply melting and mixing PP homopolymers with externally produced elastomers such as ethylene-propylene (EPR) and ethylene-propylene-diene elastomers (EPDM) in various amounts at 0 ° C. Overcame the critical glass transition temperature (Tg) of PP up to, and gradually developed into its own science and technology. Different phase (impact) propylene copolymers can be produced by using advanced catalysts (Ziegler-Natta catalyst (ZN), metallocene catalyst, geometrically constrained catalyst, etc.) as well as controlled particle morphology in the multistage polymerization process. It became. Utilization of these polyphase PP copolymers, along with crystalline PP matrices and dispersed amorphous EP elastomer phases, is no longer limited to the technical and automotive fields, but for pipe materials and a wide range of advanced packaging solutions. Also includes. "Block copolymers" are manufactured in multi-reactor vapor phase plants, such as bulk / vapor phase combinations such as the Spheripol method and the Borstar PP PP method. A grade that combines a crystalline PP matrix (produced in the first 1-2 reactors) with embedded particles of EPR and PE (produced in one or more reactors described below) that define impact resistance and low temperature resistance. Later came to be called heterophase copolymers or impact copolymers. In addition to the crystalline PP matrix and amorphous EPR, the reactor impact copolymer has a crystallinity of both PP and PE crystallizable segments and a uniform medium density PE copolymerized with C3. Polymers can be found. The elucidation of this complex structure is progressing by combining cross fractionation with various techniques that correlate molecular structures with the performance of these materials. This greatly affects the phase behavior and interfacial adhesion between the matrix and the dispersed phase.

The size, shape, internal structure and spatial packing of the distributed domain are important parameters that affect not only mechanical performance but also properties such as surface appearance, transparency and mobility. This "phase morphology" is a complex result of component rheology, compatibility between matrix and dispersed phases, and processing conditions. Variations in EPR composition have been shown to affect all three.

Simply increasing the EPR weight fraction of the PP impact copolymer is a common approach for improving toughness by reducing the interparticle distance and increasing the energy absorption capacity. In fact, a stepwise transition from brittleness to toughness is observed as a function of EPR concentration.

Post-reactor modification: Historically, PP has been a variety of impact modifiers such as EPR, EPDM, or polystyrene-block-poly (ethylene-co-but-1-ene) -block-polystyrene (SEBS). Has been mixed with to improve impact behavior and generally balance the property profiles of these materials. The development of new methods and catalysts has made it possible to prepare these materials in-situ, and the resulting system is very complex in structure, and the relationship between structure and properties. Advanced analysis is required to establish.

The higher the compatibility of the components, the higher the impact altitude at room temperature.

Further possible is, for example, reactor-grade chemical modification or decomposition in radical reactions initiated by peroxides. Depending on the temperature during the radical reaction and the presence of co-agents, graft PP, branched PP, or degraded (bisbroken) PP can be obtained. Decomposition or bisbraking caused by peroxides is often used to enhance the flow properties of PP.

When PP homopolymers are used as the base material, the combination of radical modification and recombination in the presence of a coupling agent results in high melt strength PP with long chain branching. When the impact copolymer is the base material, the reactive modified copolymer can be obtained in the same way. By adding a free radical initiator and an auxiliary agent such as diene, ethylene-propylene grafted on PP is formed. This strengthens the interface between the PP matrix and EPR particles and reduces the tendency of the particles to aggregate. These materials exhibit improved morphology and significantly increased impact strength.

WO2012049690A1 describes a method for preparing a high melt strength propylene polymer. This method of preparation is carried out with the base in the presence of 10-50 ppm of organic peroxide and 0.2-20 w / w% of additives such as stabilizers, acid neutralizers, antioxidants or lubricants. The propylene polymer is mixed with 0.1 to 1 w / w% of the polyfunctional acylate monomer.

US20130059958A1 deals with a method of modifying a propylene polymer by melt grafting of polyfunctional monomers (PFMs), including a pre-start step. By this method, branching is introduced into the propylene polymer matrix by promoting complete absorption of PFMs on the polymer matrix and initiating grafting prior to reaction extrusion without the use of free radical initiators. can do

US20070004864A1 relates to a polypropylene composition and a method for preparing the composition. The method is at least one isotactic polypropylene, at least one impact resistant modified polymer, a monofunctional monomer, at least one primary aid, a polyfunctional monomer, an oligomer or a polymer. Includes steps to mix and extrude the secondary aid and radical initiator. This composition can be prepared in an extruder.

WO2016014122A1 relates to (a) a heterophase polymer composition comprising a propylene polymer phase comprising a propylene polymer selected from the group consisting of propylene homopolymers, propylene copolymers and one or more comonomer up to 50% by weight.

WO2015138300A1 contains (a) a heterogeneous phase containing a propylene polymer phase containing a propylene homopolymer, a propylene copolymer, and a propylene polymer selected from the group consisting of up to 50% by weight of ethylene or C4-10 α-olefin monomer. With respect to polymer compositions.

WO2010009825A1 is prepared by adding at least one kind of organic peroxide and polyfunctional acrylicate as an auxiliary agent so that the ratio of peroxide / auxiliary agent is 1: 0.4 to 1: 5, and acid. The present invention relates to a method for producing a modified polypropylene composition, which comprises the step of adding a sweeping agent.

Considering the above discussion, it is clear that the challenge of heterophase impact copolymers is to maintain a proper balance between impact strength and flexural modulus in addition to a melt flow index higher than 100 dl / min. Therefore, in the present invention, the problem of obtaining a PP composition having the highest no-break impact resistance with a higher melt flow without affecting the flexural modulus is solved.

It is an object of the present invention to provide a morphologically modified heterophase polymer and to be novel and economical for morphological modification of heterophase polypropylene copolymers using polyfunctional additives and organic peroxides. Is to provide a method. A further object of the present invention is to provide morphological modification of a different phase copolymer of polypropylene, which is a novel and economical method for preparing a morphological modifier composition and a reactor. Includes post-extrusion processes. Another object of the present invention is to provide a morphologically modified product useful for injection molding, thin wall injection molding, compounding applications and the like.

Therefore, the present invention provides a morphologically modified heterophase polymer in which the heterophase polymer comprises the following two different phases. The morphologically modified heterophase polymer includes a first phase and a second phase. The first phase is a propylene polymer phase containing homopolypropylene, a copolymer of propylene and ethylene, and optionally C4 to C10 alpha olefins, with a propylene content of 90 to 95% by weight in the propylene polymer phase. is there. The second phase is an ethylene polymer phase containing homopolyethylene and a copolymer of ethylene and C3 to C10 alpha olefin, and the ethylene content in the ethylene polymer phase is 20 to 50% by weight. The morphologically modified heterophase polymer has a no-break impact strength of 500 J / m to 700 J / m according to ASTM standard D256, a high melt flow index of 3 to 150 g / 10 minutes according to ASTM D1238, and balanced according to ASTM standard D790. ) It has a flexural modulus of 700 to 1400 MPa.

As one of the features of the present invention, the morphologically modified heterophase polymer has no-break impact strength as defined by a notched Izod test measured at room temperature. As another feature of the present invention, the morphologically modified heterophase polymer has an equilibrium flexural modulus up to 1800 MPa.

Another feature of the present invention is that the ethylene content of the morphologically modified heterophase polymer is 5 to 75% by weight, preferably 8 to 20% by weight.

Another feature of the present invention is that the propylene content of the morphologically modified heterophase polymer is 90-95% by weight.

As one of the features of the present invention, C4 to C10 alpha olefins are selected from the group consisting of 1-butene, 1-hexene, 1-pentene, 1-octene and 1-decene.

Another feature of the present invention is that C3-C10 alphaolefins are selected from the group consisting of 1-propene, 1-butene, 1-hexene, 1-pentene, 1-octene and 1-decene.

Yet another feature of the present invention is that the ethylene concentration in the propylene polymer phase is 5-50%.

Another feature of the present invention is that in the morphologically modified heterophase polymer, either the ethylene phase or the propylene phase constitutes a continuous phase and a discrete phase of a heterogeneous polymer system. The concentrations of the ethylene phase and the propylene phase may vary greatly depending on the concentration of the discrete phase or the dispersed phase.

In yet another embodiment, the ethylene polymer phase can be prepared with an ethylene propylene copolymer or an ethylene octane-based elastomer.

The present invention also provides a method of preparing a morphologically modified heterophase polymer. In this method, (i) a polyfunctional additive and a peroxide are premixed in an organic solvent to obtain a morphological modifier composition, and the morphological modifier composition is mixed with a heterophase polymer. It comprises the steps of obtaining a mixed composition and (ii) extruding the premixed composition to obtain a morphologically modified heterophase polymer.

As one of the features of the present invention, in the method of preparing a morphologically modified heterophase polymer, the premixed composition is extruded by a twin-screw extruder (TSE) at a temperature of 160 to 300 ° C.

Another feature of the present invention is that in the method for preparing a morphologically modified heterophase polymer, the polyfunctional additive is an unsaturated organic vinyl compound from pentaerythritol triacrylate, pentaerythritol tetraacrylate and butanediol diacrylate. Selected from the group of

As yet another feature of the present invention, in the method for preparing a morphologically modified heterophase polymer, the amount of the polyfunctional additive added is 1000 to 7500 ppm.

As yet another feature of the present invention, in the method of preparing a morphologically modified heterophase polymer, the peroxide is selected from the group comprising alkyl peroxides and peroxyesters.

As yet another feature of the present invention, the amount of peroxide added in the method for preparing a morphologically modified heterophase polymer is 25 to 2000 ppm.

As yet another feature of the present invention, in the method of preparing a morphologically modified heterophase polymer, the organic solvent is selected from the group consisting of acetone, dichloromethane (DCM), paraffin oil, and ethanol.

As yet another feature of the present invention, in the method for preparing a morphologically modified heterophase polymer, the amount of the organic solvent added is 0.5 to 60 ml / kg.

As yet another feature of the present invention, in the method for preparing a morphologically modified heterophase polymer, premixing is performed at 10 to 35 ° C. or at a temperature not exceeding the boiling point of an organic solvent, peroxide, or polyfunctional additive. ..

Yet another feature of the present invention is the premixing for 2 to 30 minutes in the method of preparing a morphologically modified heterophase polymer.

One of the features of the present invention is that in the method of preparing a morphologically modified heterophase polymer, step (i) comprises adding an antioxidant, acid scavenger and nuclear additive additive package.

One of the preferred features of the present invention is that in the method of preparing a morphologically modified heterophase polymer, the heterophase polymer has two different phases. The heterogeneous polymer has a first phase and a second phase. The first phase is a propylene polymer phase containing homopolypropylene, a copolymer of propylene and ethylene, and optionally C4-C10 alpha olefin, with a propylene content of 90-95% by weight in the propylene polymer phase. is there. The second phase is an ethylene polymer phase containing homopolyethylene and a copolymer of ethylene and C3 to C10 alpha olefin, and the ethylene content in the ethylene polymer phase is 20 to 50% by weight.

Yet another feature of the present invention is that in the method of preparing a morphologically modified heterophase polymer, the heterophase polymer has two different phases: (i) homopolypropylene and (ii) a copolymer of ethylene and propylene. .. The heterophase polymer is produced in a two-step process, with homopolypropylene polymerization in the first reactor and ethylene propylene rubber polymerization in the second reactor.

Yet another feature of the present invention is that in the method of preparing morphologically modified heterophase polymers, the polymerization is carried out in the presence of a Ziegler-Natta or metallocene catalyst.

As yet another feature of the present invention, in the method for preparing a morphologically modified heterophase polymer, the ethylene content of the ethylene propylene copolymer is 10 to 80% by weight.

Yet another feature of the present invention is that in the method of preparing a morphologically modified heterophase polymer, the ethylene content in the heterophase polymer is 8 to 20%.

Another feature of the present invention is that in the method for preparing a morphologically modified heterophase polymer, the xylene content of the heterophase polymer according to ASTM D5492 is 10-30% by weight, and the melt flow index (MFI) according to ASTM D1238 is 10-100 g / g. It takes 10 minutes, the flexural modulus according to ASTM standard D790 is 700 to 1300 MPa, and the impact strength determined by the notched eyezod method measured at room temperature according to ASTM standard D256 is 80 to 700 J / m.

One of the features of the present invention is that the morphologically modified heterophase polymer brings about improved properties of high fluidity and high impact resistance.

Another feature of the present invention is that in the method of preparing a morphologically modified heterophase polymer, the premixed composition is extruded in a twin-screw extruder at a temperature of 160-300 ° C. As one of the preferred features, the premixed composition is extruded in a twin-screw extruder at 100-280 ° C.

As a preferred feature, in the method for preparing a morphologically modified heterophase polymer, the polyfunctional additive is an unsaturated organic vinyl compound consisting of pentaerythritol triacrylate, pentaerythritol tetraacrylate, and butanediol diacrylate. It is selected from. Another feature is that the amount of the polyfunctional additive added is 1000 to 7500 ppm.

Another preferred feature is that in the method for preparing morphologically modified heterophase polymers, the peroxide is selected from the group consisting of alkyl peroxides and peroxyesters. As one characteristic, the peroxides are di-tert-butyl peroxide, dicumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide, and 2,5-bis (tert-). Butylperoxy) -2,5-dimethylhexin-3, diisopropylbenzene monohydroperoxide, 2,5-bis (tert-butylperoxy) -2.5-dimethylhexane, tert-butylperoxybenzoate, and Luprox. It is selected from the group consisting of lauryl peroxides with trade names such as 101, Luplox 100, Triganox 101, and Triganox 301. Another feature is that the amount of peroxide added is 25-2000 ppm.

Another preferred feature is that in the method of preparing the morphologically modified heterophase polymer, the organic solvent is selected from the group comprising acetone, dichloromethane (DCM), paraffin oil, and ethanol. Yet another feature of the present invention is the addition of 0.5-60 ml / kg of organic solvent.

As a preferred feature, in the method for preparing the morphologically modified heterophase polymer, premixing is carried out at 10-35 ° C. or at a temperature not exceeding the boiling point of the organic solvent, peroxide or polyfunctional additive. As another preferred feature, premixing is performed for 2-30 minutes. Preferably, the premix is performed for 2 to 20 minutes. More preferably, premixing is performed for 5-10 minutes. Yet another feature is that the premixing is carried out at ambient pressure, either in the presence of an inert gas or in the presence of air.

As another preferred feature, in the method of preparing a morphologically modified heterophase polymer, step (i) comprises adding an antioxidant (primary, secondary), acid scavenger, and nuclear additive additive package. Another feature is that antioxidants are primary and secondary.

As one feature, in the method of preparing a morphologically modified heterophase polymer, the heterophase polymer has two different phases: (i) homopolypropylene and (ii) a copolymer of ethylene and propylene. The heterophase polymer is produced in a two-step process, with homopolypropylene polymerization in the first reactor and ethylene propylene rubber polymerization in the second reactor. As a preferred feature, the polymerization is carried out in the presence of a Ziegler-Natta or metallocene catalyst. As yet another feature, the ethylene content of the ethylene propylene copolymer is 10 to 80% by weight. One feature is that the ethylene content in the heterophase polymer is 8-20%. Other preferred features are that the xylene content of the heterophase polymer according to ASTM D5492 is 10-30% by weight, the melt flow index (MFI) according to ASTM D1238 is 10-100 g / 10 min, and the flexural modulus according to ASTM standard D790. Is 700 to 1300 MPa, and the impact strength determined by the Notched Izod Method measured at room temperature according to ASTM Standard D256 is 80 to 700 J / m (no break, i.e. greater than 500 J / m).

The present invention also provides a morphologically modified heterophase polymer having two different phases, a first phase and a second phase. The first phase is a propylene polymer phase, which contains homopolypropylene, a copolymer of propylene and ethylene, and optionally C4-C10 alpha olefin, and has a propylene content of 90-95% by weight in the propylene polymer phase. .. The second phase is an ethylene polymer phase, which contains homopolyethylene and a copolymer of ethylene and C3 to C10 alpha olefin, and the ethylene content in the ethylene polymer phase is in the range of 20 to 50% by weight. Morphologically modified heterophase polymers have a no-break impact strength of 500 J / m to 700 J / m according to ASTM standard D256, a high melt flow index of 3 to 150 g / 10 minutes according to ASTM D1238, and an equilibrium of 700 to 1400 MPa according to ASTM standard D790. Has a flexural modulus. The morphologically modified heterophase polymer is obtained by premixing a polyfunctional additive and a peroxide in an organic solvent to obtain a morphologically modifying agent composition, and by mixing the morphologically modified agent composition with the heterogeneous polymer. It can be obtained by obtaining a premixed composition and extruding the premixed composition.

Various modifications and alternative forms of the present invention are possible, and specific embodiments thereof will be described in detail below. It is understandable, of course, that the present invention is not intended to be limited to the particular forms disclosed, but rather all variants within the scope of the invention as defined by the appended claims. Includes equivalent and alternative forms.

The following description is merely exemplary embodiment and is not intended to limit the scope, applicability, or configuration of the present invention. Rather, the following description provides suitable examples for carrying out exemplary embodiments of the invention. Various changes to the described embodiments may be made in the function and arrangement of the described components without departing from the scope of the invention.

The present invention is intended to provide a novel and economical method for morphological modification of heterophase polypropylene copolymers using polyfunctional additives and organic peroxides. Morphological modification involves enhancing the interaction between the rubber phase of the polypropylene impact copolymer and the homopolymer matrix of the polypropylene impact copolymer. As a result, as the melt flow characteristics of the resin after the reactor increase several times, the impact resistance of the modified resin after the reactor is strengthened several times.

The present invention relates to morphological modification of polypropylene heterophase copolymers and involves novel and economical methods of preparing morphological modifier compositions and extrusion molding processes after the reactor.

polymer:
The heterophase polymer described in the present invention has two different phases, namely homopolypropylene produced in a two-step process and a copolymer of ethylene and propylene. The polymerization of homopolypropylene may be carried out in the first reactor, the ethylene propylene rubber polymerization may be carried out in the second reactor, and the polymerization may be carried out in the third reactor as well, if necessary. The catalyst used in this polymerization process can be a Ziegler-Natta catalyst or a metallocene catalyst. The proportion of ethylene in the ethylene-propylene copolymer is 10 to 80% by weight. The ethylene content of the final heterophase polymer according to ASTM D5492 is 8-20% and the xylene content of the resulting polymer is 10-25% by weight. The MFI of the heterogeneous polymer according to ASTM D1238 is 3-12 g / 10 min. The flexural modulus of the heterophase polymer according to ASTM standard D790 is 700 to 1300 MPa, and the impact characteristic specified by the notched Izod method measured at room temperature according to ASTM standard D256 is 80 to 700 J / m. The heterophase polymer described in the present invention is used in powder form or granulated form outside the reactor.

Method:
The method of the present invention comprises two stages. Stage 1 includes the preparation of the morphological modifier composition and the step of mixing the reactive modifying additive / morphological modifier composition with the heterophase polymer. Stage 2 includes a reaction extrusion process, where the final mixture obtained in stage 1 is extruded at 150 ° C. to 260 ° C. in a twin-screw extruder.

Stage 1
Morphological Modifier / Reactive Excipient Mixture / Morphological Modulator Composition:
Premixing the polyfunctional additive and peroxide in an organic solvent (eg acetone, DCM, paraffin oil, ethanol) 0-100 ml / kg, preferably 5-40 ml / kg, more preferably 5-20 ml / kg. In the range of 10 to 35 ° C., or at a temperature not exceeding the boiling point of the organic solvent, peroxide, or polyfunctional additive. Premixing is carried out for 2 minutes or longer, preferably 5 minutes or longer, more preferably 10 minutes or longer, particularly 30 to 45 minutes or longer. Premixing is carried out at ambient pressure, either in the presence of an inert gas or in the presence of air.

The morphological modifier composition thus prepared is added to polyolefins such as heterophase polypropylene (copolymers containing random copolymers and block copolymers). When the morphological modifier composition obtained by the above method is added to a polyolefin reactor powder or granule in a liquid supply system of a batch mixer / high-speed mixer or a twin-screw extruder, it is in a liquid state. You may use it.

Premix of impact copolymer PP powder reactor powder with PETA (pentaerythritol triacrylate) and peroxide solution, along with antioxidant, acid sweeping agent and nuclear additive additive packages, at room temperature. Under ambient pressure, the average residence time in a high speed mixer is 5 to 30 minutes or longer, more preferably 2 minutes or longer.

Antioxidants (primary, secondary), acid sweeping agents, and nuclear additive additives packages, along with a mixture of polypropylene reactor powder and reactive modifying additives, at ppm levels (750, 750) in a high speed mixer. It is added when mixing at 350 p and 250 ppm, respectively. On the other hand, the impact copolymer polypropylene granules contain this unique additive package that is added during the extrusion molding step of the manufacturing process.

The primary and secondary antioxidants used in this experiment were tetrakismethylene [3,5-di-tert-butyl-4-hydroxyhydroconnamate] methane (Irganox® 1010) and Tris (2,4). It is a combination of −di-tert-butylphenyl) phosphate (Irganox 168). The nucleating agent used here is HPN20E and the acid sweeping agent used in these experiments is calcium stearate.

The amount of the primary and secondary antioxidants added is 250 ppm to 1%, preferably 250 to 5000 ppm, and more preferably 250 to 1500 ppm. The amount of the nucleating agent and the acid sweeping agent added is 250 ppm to 2%, preferably 250 to 5000 ppm, and more preferably 250 to 1500 ppm.

Stage 2-Reactive extrusion process:
The premixed mixture is then melt-mixed in a Labtech twin-screw extruder with a maximum screw speed of 800 rpm, a screw diameter of 26 mm and a length / diameter ratio of 40: 1. did. The speed of the extruder was maintained at 100-200 rpm, the barrel temperature was maintained at 100-250 ° C, and the supply rate was maintained at 8-20 kg / hour. The modified batch extruded product was cooled in a water bath and then pelletized into 2-3 mm sized pellets.

The composition obtained according to the present invention can be used in a specific form, preferably as pellets when added to the final compounding process. The composition thus obtained may be used as a fine powder.

As one of the features of the present invention, the morphologically modified heterophase polymer has a no-break impact strength, an equilibrium flexural modulus, and a very high melt flow index of 100 g / 10 min (but not limited to this). It has PP with improved impact strength. This morphologically modified heterophase polymer was developed by modifying PP produced using conventional Ziegler-Natta catalysts and conventional methods. In that method, the impact strength is limited to 100 J / m, the MFI is limited to 10 g / min, and the flexural modulus is moderately limited. This modification improves both the melt flow index and the impact strength at the same time. This modification can be carried out in a conventional extruder used in the polymer industry, by adding a polyfunctional compound in the presence of an activator such as a peroxide or a reaction stabilizer such as a diluent. ..

The above-mentioned morphologically modified heterophase polymer is also a sample that has passed the FDA and REACH regulations.

Another feature of the present invention is that the heterogeneous polyolefin polymer consists of two different phases, the first phase is the propylene polymer phase, which is a propylene and ethylene homopolymer and a copolymer or a homozygous for C4-C10 alpha olefins. It is composed of a polymer and a copolymer, and the ethylene concentration can be up to 50%. The second phase is an ethylene polymer phase, which consists of ethylene and C3-C10 alphaolefin homopolymers and copolymers.

The ethylene polymer phase may consist only of ethylene or a copolymer of ethylene and C3 to C10 alpha olefins, based on which the ethylene content may vary between 8 and 90% by weight. ..

Here, either the ethylene phase or the propylene phase constitutes a continuous and discrete phase of the heterogeneous polymer system. The concentrations of the ethylene phase and the propylene phase may vary greatly depending on the concentration of the discrete phase or the dispersed phase.

The propylene content of the propylene polymer phase can be 80% or more, and the ethylene content in the heterophase composition can be 5 to 75% by weight. Similarly, the ethylene polymer phase may consist of an ethylene propylene copolymer or an ethylene octane-based elastomer.

The following non-limiting examples describe the invention in detail. However, they are not intended to limit the scope of the invention in any way.

Example
polymer:
PP1A is a reactor powder / heterophase polymer of a copolymer of propylene and ethylene, having an MFR2 (230 ° C.) of 9 to 11 g / 10 minutes, an ethylene content of 14 to 15%, and a xylene-soluble amount of 21 to 21. It is 23% by weight, has a flexural modulus of 800 to 1000 MPa, and has a notched eyezod impact strength of more than 500 J / m.

PP1B is an extruded granulated product of a copolymer of propylene and ethylene, having an MFR2 (230 ° C.) of 9 to 11 g / 10 minutes, an ethylene content of 14 to 15%, and a xylene-soluble amount of 21 to 23% by weight. The bending elastic modulus is 800 to 1000 MPa, and the impact strength of the notched eyezod is larger than 500 J / m.

PP2A is a reactor powder of a copolymer of propylene and ethylene, and has an MFR2 (230 ° C.) of 7 to 9 g / 10 minutes, an ethylene content of 8.5 to 10.5%, and a xylene-soluble content of 18. It has a flexural modulus of about 20% by weight, a flexural modulus of 1000 MPa to 1200 MPa, and a notched eyezod impact strength of 100 to 200 J / m.

PP2B is an extruded granulated product of a copolymer of propylene and ethylene, having an MFR2 (230 ° C.) of 7 to 9 g / 10 minutes, an ethylene content of 8.5 to 10.5%, and a xylene-soluble content of 18. ~ 20% by weight, flexural modulus of 1000 MPa to 1200 MPa, and notched eyezod impact strength of 100 to 200 J / m.

PP3A is a reactor powder of a copolymer of propylene and ethylene, and has an MFR2 (230 ° C.) of 9 to 12 g / 10 minutes, an ethylene content of 8 to 10%, and a xylene-soluble amount of 16.5 to 19. It is 5.5% by weight, has a flexural modulus of 1000 MPa to 1200 MPa, and has a notched eyezod impact strength of 100 to 200 J / m.

PP3B is an extruded granulated product of a copolymer of propylene and ethylene, and has an MFR2 (230 ° C.) of 9 to 12 g / 10 minutes, an ethylene content of 8 to 10%, and a xylene-soluble amount of 16.5 to 19. It is 5.5% by weight, has a flexural modulus of 1000 MPa to 1200 MPa, and has a notched eyezod impact strength of 100 to 200 J / m.

PP4 is a reactor powder of a copolymer of propylene and ethylene, and has an MFR2 (230 ° C.) of 3 to 4 g / 10 minutes, an ethylene content of 9 to 10%, and a xylene-soluble amount of 15.5 to 18 It is 5.5% by weight, has a flexural modulus of 1000 MPa to 1200 MPa, and has an impact strength of more than 150 J / m.

Chemical product details:
Details of the chemical products used in the examples are as follows.
● Peroxide 1-Luperox 101 (2,5-dimethyl-2,5-di (tert-butylperoxy) hexane) molecular weight 290 g / mol, 0.877 g / ml, and assay 90%.
● Peroxide 2-Triganox 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-tripeloxonan)
● The MFC1-PETA (pentaerythritol triacryllate) used contains 298.29 g / mol in molecular weight, 1.18 g / ml at 25 ° C., and 300 to 400 ppm monomethyl ether hydroquinone as a reaction inhibitor.
● MFC2-PeteA (Pentaerythritol Tetraacrylate)
● Solvent 1-The purity of acetone used is 99%, the weight per 1 ml at 20 ° C is 0.79 to 0.792 g, the upper limit of impurities of non-volatile substances is 0.002%, and the acidity is 0.015%. And 0.4% water
● Solvent 2-DCM (dichloromethane)
● Solvent 3-The LP (liquid paraffin light) used has a viscosity of 25 to 80 mPas at 25 ° C, a weight of 0.82 to 0.88 g per ml at 25 ° C, and a maximum impurity of water of 0.05%.

Experiment details:
Samples for mechanical testing according to ASTM standards were prepared using the pelleted composition of the reaction extrusion process. This preparation was performed by an injection molding machine manufactured by L & T Plastic Machinery Co., Ltd. with a screw diameter of 40 mm, an L: D ratio of 20: 1, and a mold clamping force of 60 tonnage. The barrel temperature was kept at 150 ° C. to 300 ° C., and the mold temperature was kept at 60 ° C. The resulting injection molded sample was used to measure tensile, flexing, and impact strength according to ASTM standards.

The melt flow rate of the compounded sample was measured according to ASTM D1238 with an automatic multiload MFI device manufactured by Gottfret at 230 ° C. and a load of 2.16 kg.

The flexural modulus was adjusted according to the ASTM D618 standard and then measured according to ASTM D790 with a universal testing machine manufactured by TIRA (Germany).

The notched Izod impact strength of the bar was adjusted according to ASTM D618 standard and then measured at 23 ° C. according to ASTM D256.

The yellowness index is a numerical value calculated from spectrophotometric data and represents the color change of the test sample from transparent or white to yellow. This test is most commonly used to assess the color change of a substance caused by actual or simulated outdoor exposure. The yellowness index of the extruded granules was measured at 23 ° C. by Labscan XE from Hunterlab according to ASTM E 313-10.

Example 1:
The following examples show the reactive modification of impact copolymer polypropylene reactor powder (PP3A) using various reactive morphological modifier compositions and the properties enhanced by the method of the present invention. Is.

Table 1: Shows the various mixtures used in the reaction extrusion of PP3.

Test samples with all of the above formulations were prepared and tested for physical properties of the samples according to the above ASTM standards. Example 1 and Example 17 are both plant-derived pure polypropylene materials, but with different production lots.

The table below shows the melt flow index (g / 10 min) of the modified batch in polypropylene PP3A at 230 ° C., 2.16 kg load, impact strength according to ASTM D256 (J / m), and ASTM D 790. Therefore, the flexural modulus (MPa) is shown.

For the above test, PP3A reactor powder (Experiment (EXP) 1) having an MFI of 11 g / 10 minutes and an impact strength of about 115 J / m was used. Experiment 1 is a comparative example in which peroxide and MFC were not added and the treatment was performed with TSE under the same treatment conditions as those described in the reaction extrusion molding process.

In Experiments 2-16, combining a low concentration, ie 25-100 ppm peroxide, with a higher concentration MFC of 2500-7500 ppm gave higher impact strengths above 500 J / m, but MFI. Was maintained at 8-15 g / 10 min. That is, the flow characteristics did not change.

However, in Experiments 20-29, by combining a peroxide having a concentration of 100-200 ppm and an MFC having a concentration of 1000-5000 ppm, a high MFI of 16-22 and 500 J were maintained while maintaining a flexural modulus of 800-1060 MPa. An impact strength exceeding / m was obtained.

Example 2:
The following examples showed reactive modification of impact copolymer polypropylene extruded granules (PP3B) using various reactive morphological modifier compositions, and enhanced properties by the methods of the invention. It is a thing.

Test samples with all of the above formulations were prepared and tested for physical properties of the samples according to the ASTM standards described above.

The table below shows the melt flow index (g / 10 min) of a modified batch in polypropylene PP3B at 230 ° C., 2.16 kg load, impact strength according to ASTM D256 (J / m), and ASTM D 790. Therefore, the flexural modulus (MPa) is shown.

For the above test, a PP3B extruded granulated material with an MFI of 11 g / 10 min and an impact strength of about 100 J / m was used (Experiment 38). Experiment 38 is a comparative example treated with TSE under the same treatment conditions as described in the reaction extrusion process without the addition of peroxide and MFC.

Morphological modification was performed with PP3B (used in Experiment 38) with the addition of 100-200 ppm peroxide and 2500-7500 ppm MFC (see Experiments 40, 41 and 76-78). As a result, the MFI was 18 to 20 g / 10 minutes, and the impact strength was larger than 500 J / m, that is, there was no break.

However, in Experiment 39 with the addition of lower concentrations (ie 50 ppm) of peroxide and MFC with a concentration of 5000 ppm, there was no break (ie, impact strength above 500 J / m) and MFI was reduced (ie 6). The result was .7 g / 10 minutes).

Example 3:
The following examples showed reactive modification of impact copolymer polypropylene reactor powder (PP2A) using various reactive morphological modifier compositions, and enhanced properties by the methods of the invention. It is a thing.

Test samples with all of the above formulations were prepared and tested for physical properties of the samples according to the above ASTM standards. Experiment 42 is a virgin polypropylene material. That is, no additives have been added. It was extruded by TSE and left as a reference. That is, it is a PP2A material.

The table below shows the melt flow index (g / 10 min) of the modified batch in polypropylene PP2A at 230 ° C., 2.16 kg load, impact strength according to ASTM D256 (J / m), and ASTM D 790. Therefore, the flexural modulus (MPa) is shown.

PP2A reactor powder with MFI of 8 g / 10 minutes and impact strength of 300 J / m (Experiment 42). Experiment 42 is a comparative example of treatment with TSE under the same treatment conditions as those described in the reaction extrusion process without the addition of peroxide and MFC.

As a result of using PP2A reactor powder (used in Experiment 42) with MFI of 8 g / 10 min and impact strength of 300 J / m, a peroxide of 200 to 500 ppm was used in combination with a low concentration of 2500 ppm MFC. The MFI when morphologically modified was 15 to 22 (Experiments 43 to 51).

Example 4:
The following examples show the reactive modification of impact copolymer polypropylene granules (PP2B) using various reactive morphological modifier compositions, and the properties enhanced by the methods of the invention.

Test samples with all of the above formulations were prepared and tested for physical properties of the samples according to the above ASTM standards.

The table below shows the melt flow index (g / 10 min) of a modified batch in polypropylene PP2B at 230 ° C., 2.16 kg load, impact strength according to ASTM D256 (J / m), and ASTM D 790. Therefore, the flexural modulus (MPa) is shown.

For the above test, a PP2B granulated product having an MFI of 9 g / 10 minutes and an impact strength of about 150 J / m was used (Experiment 54). Experiment 54 is a comparative example of treatment with TSE under the same treatment conditions as described in the reaction extrusion process without the addition of peroxide and MFC.

Experiments (55-56, 79-81) were performed with 250-300 ppm peroxide and 2500-3000 ppm MFC. As a result, an extruded granule having an MFI of 18 to 22 g / 10 minutes and an impact strength of more than 500 J / m, that is, a no-break extruded granule was obtained.

Experiments (82-84) were performed with 500-1500 ppm peroxide and 2000-3000 ppm MFC. As a result, the MFI was 27 to 60 g / 10 minutes, and the impact strength was greater than 500 J / m, that is, a non-breaking extruded granule was obtained.

Example 5:
The following examples show the reactive modification of impact copolymer polypropylene reactor powder (PP1A) using various reactive morphological modifier compositions, and the properties enhanced by the methods of the invention.

Test samples with all of the above formulations were prepared and tested for physical properties of the samples according to the above ASTM standards.

The table below shows the melt flow index (g / 10 min) of the modified batch in polypropylene PP1A at 230 ° C., 2.16 kg load, impact strength according to ASTM D256 (J / m), and according to ASTM D790. It shows the flexural modulus (MPa).

For the above test, a PP1A material having an MFI of 11.5 g / 10 minutes and an impact strength of 630 J / m (no break) was used (Experiment 57). Experiment 57 is a comparative example of treatment with TSE under the same treatment conditions as described in the reaction extrusion process without the addition of peroxide and MFC.

Experiments 65 and 66 were performed using PP1A material with a peroxide of 350 ppm and an MFC of 2500 ppm. As a result, the MFI was 25 to 30 g / 10 minutes, and there was no break.

In the experiments (59-64), the MFI was higher, but the impact strength was as low as 100-150 J / m.

Example 6:
The following examples show the reactive modification of impact copolymer polypropylene extruded granules (PP1B) using various reactive morphological modifier compositions, and the properties enhanced by the methods of the invention.

Test samples with all of the above formulations were prepared and tested for physical properties of the samples according to the above ASTM standards.

The table below shows the melt flow index (g / 10 min) of the modified batch in polypropylene PP1B at 230 ° C., 2.16 kg load, impact strength according to ASTM D256 (J / m), and according to ASTM D790. It shows the flexural modulus (MPa).

Experiments 90-92 were conducted to determine the effect of solvent amount on final properties such as MFI and impact strength. The peroxide used in these three experiments (Experiments 90-92) is 500 ppm and the MFC is 2500 ppm. The solvent was used in the range of 5 ml / kg, 10 ml / kg and 15 ml / kg (Experiments 90, 91 and 92, respectively). It was observed that as the amount of solvent increased, the MFI increased and the impact on impact properties was negligible. This indicates that the mixing properties of the premixed composition improve with increasing solvent content. Experiments 87-89 were also performed to determine the effect of the solvent on the final properties. Similar correlations exist in this experiment using 500 ppm peroxide and 3000 ppm MFC. Again, it was observed that the MFI increased with increasing solvent content and had little effect on impact properties.

Experiments 93-97 were performed with higher concentrations of peroxide (1500-2000) ppm and MFC at concentrations of 800-1500 ppm. As a result, the material has a very high fluidity of 100 g / 10 minutes, and the impact strength is larger than 500 J / m, that is, no break.

Experiments 65-75 and 85-86 were carried out using peroxides at concentrations of 350-800 ppm and MFCs at concentrations of 2000-2500 ppm.

Advantages of the Invention The following are the technical advantages of the present invention over the prior art disclosed above.
● Achieve impact resistance and high fluidity from existing impact copolymer polypropylene (ICP) manufactured by conventional technology.
● Melt flow index (MFI) and impact strength can be increased at the same time without significantly affecting the flexural modulus.
● An economically viable alternative solution for producing thermoplastic olefins (TPOs) from PPs produced by conventional methods.

Claims (13)

A morphologically modified heterophase polymer with two different phases, ie
A propylene polymer phase containing homopolypropylene, a copolymer of propylene and ethylene, and C4 to C10 alpha olefin, if necessary, and the propylene content in the propylene polymer phase is 90 to 95% by weight. When,
It is an ethylene polymer phase containing a homopolyethylene and a copolymer of ethylene and C3 to C10 alpha olefin, and has a second phase in which the ethylene content in the ethylene polymer phase is 20 to 50% by weight.
The no-break impact strength according to ASTM standard D256 is 500 J / m to 700 J / m, the high melt flow index according to ASTM D1238 is 3 to 150 g / 10 minutes, and the equilibrium flexural modulus according to ASTM standard D790. A morphologically modified heterophase polymer characterized in that the value is 700 to 1400 MPa. A method for preparing a morphologically modified heterophase polymer,
(I) The polyfunctional additive and the peroxide are premixed in an organic solvent to obtain a morphological modifier composition, and the morphological modifier composition is mixed with a heterophase polymer to obtain a premixed composition. Steps to get and
(Ii) A method comprising extruding a premixed composition to obtain a morphologically modified heterophase polymer. The method according to claim 2, wherein the premixed composition is extruded by a twin-screw extruder at a temperature of 160 to 300 ° C. The method according to claim 2, wherein the polyfunctional additive is an unsaturated organic vinyl compound and is selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetraacryllate and butanediol diacrylate. A method characterized by. The method according to claim 2, wherein the amount of the polyfunctional additive added is 1000 to 7500 ppm. The method according to claim 2, wherein the peroxide is selected from the group consisting of an alkyl peroxide and a peroxy ester. The method according to claim 2, wherein the amount of peroxide added is 25 to 2000 ppm. The method according to claim 2, wherein the organic solvent is selected from the group consisting of acetone, dichloromethane (DCM), paraffin oil, and ethanol. The method according to claim 2, wherein the amount of the organic solvent added is 0.5 to 60 ml / kg. The method according to claim 2, wherein the premixing is carried out at a temperature in the range of 10 to 35 ° C. or a temperature not exceeding the boiling point of the organic solvent, peroxide or polyfunctional additive. how to. The method according to claim 2, wherein the premixing is performed for 2 to 30 minutes. 2. The method of claim 2, wherein step (i) comprises adding an antioxidant, an acid scavenger, and a nuclear additive additive package. The method of claim 2, wherein the heterogeneous polymer has two different phases, i.e.
A propylene polymer phase containing homopolypropylene, a copolymer of propylene and ethylene, and C4 to C10 alpha olefin, if necessary, and the propylene content in the propylene polymer phase is 90 to 95% by weight. When,
It is an ethylene polymer phase containing homopolyethylene and a copolymer of ethylene and C3 to C10 alpha olefin, and is characterized by having a second phase in which the ethylene content in the ethylene polymer phase is 20 to 50% by weight. how to.